Interception of a Rautenstrauch intermediate by alkynes for [5+2] cycloaddition: rhodium-catalyzed cycloisomerization of 3-acyloxy-4-ene-1,9-diynes to bicyclo[5.3.0]decatrienes

Abstract

Rholling in the bicycles: a rhodium(I)-catalyzed cycloisomerization for the synthesis of bicyclic compounds containing a cycloheptatriene ring from linear alkenynes (see scheme; cod=1,5-cyclooctadiene) is proposed to proceed through 1,2-acyloxy migration, 6 π electrocyclization, migratory insertion, and reductive elimination. The overall process can be viewed as a novel intramolecular [5+2] cycloaddition with concomitant 1,2-acyloxy migration.